The present invention relates to resilient thermoplastic multilayer films having at least two layers. The multilayer films of the present invention have at least one first layer (1) of thermoplastic polyurethane, and at least one second layer (2), which is formed from a thermoplastic elastomer with low water vapor permeability. The combination of at least one layer of thermoplastic urethane polymer and at least one layer of a thermoplastic elastomer results in a flexible multilayer film having a good mechanical property profile and a very good water vapor barrier effect.
Flexible films with good mechanical properties are required for the production of flexible filled articles filled with gaseous or liquid media, such as water beds, for example. It is known that such applications may be served by films of plasticised PVC. Given the specific properties of PVC, a relatively large amount of material has to be typically used.
It is additionally known that thermoplastic polyurethanes are used for producing flexible containers for gaseous or liquid media. Of advantage here is the high mechanical property level, whereby relatively small wall thicknesses may be achieved. A problem is the high diffusion coefficient for polar media such as water vapor, for example.
Single-layer films of thermoplastic polyurethanes (TPE-U), processes for the production thereof and the use thereof are known according to the prior art for example from EP-A-0 308 683, EP-A-0 526 858, EP-A-0 571 868 or EP-A-0 603 680. The structures described in these specifications may be incorporated into laminating films as a higher melting-point layer or layers for multilayer films or are already incorporated into the laminating films known in the art. The production of TPE-U films using substantially incompatible polymers as flatting agents in TPE-U is also described, e.g., in DE-A 41 26 499.
Multilayer, coextruded films of TPE-U and other raw materials assigned to the thermoplastics group have also been described. In addition to coextrusion with polyolefinic thermoplastics, in which the polyolefinic layer does not as a rule undergo any interlayer adhesion with regard to the TPE-U layer and merely exhibits the function of a supporting or separating layer, multilayer structures with good interlayer adhesion are also known. EP-A-0 842 768 describes, for example, a multilayer structure of TPE-U and a polyolefinic coupling agent. In the case of such structures, cracking occurs in the thermoplastic layer as a result of the low elasticity of the thermoplastics in the event of relatively frequent cyclic loads with high strain values, thereby resulting in functional impairment.
In addition to thermoplastic polyurethanes, there exist further flexible materials which are generally covered collectively by the generic term thermoplastic elastomers (TPE). Of primary importance among the groups suitable for film processing are block copolymers. These include, in addition to TPE-U, styrene-based systems (TPE-S), polyether ester types (TPE-E) and polyether block amides (TPE-A). Films based on TPE-E are described for example in U.S. Pat. No. 5,859,083, wherein particular emphasis is placed therein on high water vapor permeability. The same applies to the films of TPE-A described in EP-A-0 761 715. TPE-S suitable for films and the use thereof are described in DE-A-1 9628 834, for example. An overview of the thermoplastic elastomer group is given for example in: Thermoplastic elastomers: a comprehensive review, ed. N. R. Legge, G. Holden and H. E. Schroeder, Carl Hanser Verlag, Munich 1987 and Thermoplastische Elastomerexe2x80x94Herausforderung an die Elastomerverarbeiter, ed.: VDI-Gesellschaft Kunststofftechnik, VDI Verlag, Dxc3xcsseldorf, 1997.
The object was thus to provide a flexible film with a mechanical property profile superior to that of plasticised PVC combined with high water vapor impermeability. To minimize production costs, the combination of properties should, where possible, be obtained in a single-stage process.
In accordance with the present invention, there is provided a multilayer film comprising:
at least one first layer (1) of thermoplastic polyurethane;
at least one second layer (2) of thermoplastic elastomer; and
optionally a third layer (3) of thermoplastic polyurethane (which may be the same or different than the thermoplastic polyurethane of the first layer),
wherein the ratio of the water vapor permeability level of said first layer (1) to the water vapor permeability level of said second layer (2) is at least two, and when said optional third layer (3) is present, said first (1) and third (3) layers together enclose said second layer (2).
Other than in the operation examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term xe2x80x9cabout.xe2x80x9d
Surprisingly, the water vapor permeability of the multilayer film of the present invention are very low. If the ratio of the water vapor permeabilities of the layers (1) and (2) is increased to at least six, the water vapor permeability of the multilayer films of the present invention may be further minimized. Therefore, in a preferred embodiment of the multilayer film of the present invention, the ratio of the water vapor permeability level of the first layer (1) to the water vapor permeability level of the second layer (2) is at least six.
The first layer (1) and optional third layer (3) of the multilayer film of the present invention are each independently composed of at least one thermoplastic polyurethane elastomer, preferably of a predominantly linear thermoplastic polyurethane elastomer, the relatively long chain diol component of which is a polyester diol or polyether diol and which exhibits a Shore-A hardness of 70-95, preferably 85-95, as determined in accordance with DIN 53,505.
Suitable thermoplastic polyether/ or polyester/polyurethane elastomers and/or mixtures thereof may for example be produced by art-recognized batch and/or partially and/or fully continuous processes, in particular by the reaction in a screw extruder of the following components a) through e).
a) organic, preferably aromatic or cycloaliphatic diisocyanates;
b) polymeric diols with molecular weights of preferably 500 to 8000;
c) chain-extending components with molecular weights of preferably 60 to 400;
d) optionally in the presence of catalysts; and
e) optionally in the presence of auxiliary substances and/or additives.
Components a) through e) which may be used in the production of suitable thermoplastic polyether/ or polyester/polyurethane elastomers and/or mixtures thereof are described in further detail as follows.
a) The organic diisocyanates (a) preferably comprise aromatic or cycloaliphatic diisocyanates. In detail, the following may be mentioned by way of example: aromatic diisocyanates, such as 2,4- and 2,6-tolylene diisocyanate, 4,4xe2x80x2-, 2,4xe2x80x2- and 2,2xe2x80x2-diphenylmethane diisocyanate or mixtures thereof, cycloaliphatic diisocyanates, such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate and 4,4xe2x80x2-, 2,4xe2x80x2- and 2,2xe2x80x2-dicyclohexylmethane diisocyanate or mixtures thereof.
b) Suitable higher molecular weight diol compounds (b) with preferred molecular weights of 400 to 8000 are preferably molecules of linear structure with a low glass transition temperature or softening point. These include polyetherols and polyesterols. However, hydroxyl group-containing polymers, for example polyacetals such as polyoxymethylenes and in particular water-insoluble formals and aliphatic polycarbonates, in particular those from diphenyl carbonate and 1,6-hexanediol, produced by transesterification, are also worthy of consideration. Moreover, hydroxyl group-capped diol compounds of polyolefins, in particular aliphatic hydroxyl group-capped copolymers of ethylene and butylene are also feasible. The diol compounds have to be at least predominantly linear, i.e. of difunctional structure for the purposes of the isocyanate reaction. The above-mentioned diol compounds may be used as individual components or in the form of mixtures.
c) The chain-extending agents with molecular weights of 60 to 400, preferably 60 to 300, may preferably comprise alkane diols with 2 to 12 carbon atoms, preferably with 2, 4 or 6 carbon atoms, such as for example ethanediol, 1,6-hexanediol and in particular 1,4-butanediol, and dialkylene ether glycols, such as for example diethylene glycol and dipropylene glycol. However, diesters of terephthalic acid with alkanediols having 2 to 4 carbon atoms are also suitable, such as for example terephthalic acid bis-ethanediol or -1,4-butanediol, hydroxyalkylene ethers of hydroquinone, (cyclo-)aliphatic diamines, such as for example isophoronediamine, ethylenediamine, and aromatic diamines, such as for example 2,4- and 2,6-tolylenediamine.
d) Suitable catalysts, which accelerate in particular the reaction between the isocyanate groups of category a) and the hydroxyl groups of categories b) and c), are the conventional tertiary amines that are well known to those of ordinary skill in the art, such as for example triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,Nxe2x80x2-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo(2,2,2)octane and the like, together with in particular organic metal compounds such a titanic acid esters, iron compounds such as for example iron(III) acetylacetonate, tin compounds, such as tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like. The catalysts are conventionally used in amounts of from 0.001 to 0.2 parts per 100 parts of hydroxyl compound b).
e) In addition to catalysts, auxiliary substances and/or additives e) may also be added to the structural components a) to c). Examples of auxiliary substances and/or additives that may be used include, but are not limited to, lubricants, inhibitors, stabilizers acting with regard to hydrolysis, light, heat, oxidation or discoloration, dyestuffs, pigments, inorganic and/or organic fillers, reinforcing agents and low molecular weight plasticisers.
Suitable thermoplastic polyurethanes that may be used in the present invention include commercially available thermoplastic polyurethanes. Examples of commercially available thermoplastic polyurethanes that may be used in the present invention include, but are not limited to, those available under the trademarks DESMOPAN thermoplastic polyurethane, ELASTOLLAN thermoplastic polyurethane, ESTANE thermoplastic polyurethane, MORTHANE thermoplastic polyurethane, PELLETHANE thermoplastic polyurethane, PEARLTHANE thermoplastic polyurethane, SKYTHANE thermoplastic polyurethane, TECOFLEX thermoplastic polyurethane, and TEXIN thermoplastic polyurethane.
In a particularly suitable embodiment, the multilayer films according to the present invention comprise resilient urethane/elastomer formulation components, the soft segment phase of which consists predominantly of ether soft segment structural units. In this way, better resistance to hydrolysis is achieved. In addition, such materials exhibit better resistance to fungal and microbial attack.
To produce the second layer (2), thermoplastic elastomers are preferably used which exhibit a water vapor permeability level which lies between 0 and 150 g/cm2*d, as determined in accordance with DIN 53,122, using a 50 xcexcm thick layer of the film, at 23xc2x0 C., and 85% relative humidity. In a particularly preferred embodiment of the multilayer film according to the present invention, the thermoplastic elastomer used to produce the second layer (2) exhibits a water vapor permeability level of between 0 and 50 g/cm2*d, as determined in accordance with DIN 53,122, using a 50 xcexcm thick layer of the film, at 23xc2x0 C., and 85% relative humidity. In a yet more preferred embodiment of the multilayer film according to the present invention, the thermoplastic elastomer used to produce the second layer (2) exhibits a water vapor permeability level of between 0 and 20 g/cm2*d, preferably between 0.25 and 20 g/cm2, as determined in accordance with DIN 53,122, using a 50 xcexcm thick layer of the film, at 23xc2x0 C., and 85% relative humidity.
In a particularly preferred embodiment, styrene-based thermoplastic elastomers (TPE-S) are used in the second layer (2) of the multilayer film according to the present invention.
The TPE-S used according to the present invention consist of alternating blocks or segments, which comprise styrene monomer-based units, also known as hard segments, and softer, rubber-like units or so-called soft segments. The individual blocks conventionally consist of at least one hundred monomer units. Linear triblock structures comprising styrene/soft segment/styrene blocks are widely used. Linear, star-shaped and branched structures also exist which are based on individual or repeatedly incorporated blocks of the type comprising n styrene/soft segment blocks, where n is greater than or equal to 1.
In an embodiment of the multilayer films according to the present invention, the first layer (1), second layer (2) and optional third layer (3) each independently contain additional conventional additives selected from:
I. antiblocking agents, inorganic or organic spacers;
II. lubricants or mould-release agents;
III. pigments or fillers; and
IV. stabilizers.
The total content of the additives I through IV is preferably between 0% and 30% by weight, based on the total weight of the layer. The conventional additives which may be contained in the multilayer films according to the present invention are described by Gxc3xa4chter and Mxc3xcller, for example, in: Kunststoff-Additive, Carl Hanser Verlag Munich, 3rd edition (1989).
In a particularly preferred embodiment of the present invention, the multilayer film comprises an at least three-layer structure, characterized in that the second layer (2) containing the thermoplastic elastomer, lies between and is enclosed by at least one first layer (1) and at least one third layer (3) each independently composed of thermoplastic polyurethane.
Multilayer films preferred according to the present invention have a total thickness of between 50 xcexcm and 600 xcexcm. In such a preferred multilayer film, the thickness of the first layer (1) and optional third layer (3) of thermoplastic polyurethane is preferably and independently between 20 xcexcm and 400 xcexcm, while the thickness of the TPE second layer (2) is preferably between 10 xcexcm and 200 xcexcm.
Of particular suitability for producing the multilayer film according to the present invention are the art-recognized thermoforming processes for processing plastics to yield multilayer sheet products. An example of which includes, production by coextrusion, which preferably proceeds by the blown film process. Of the production processes suitable for producing multilayer thermoplastic sheet products, coextrusion is particularly preferred as a result of the better interlayer adhesion which may be achieved.
The surface properties of one or both sides of the multilayer films of the present invention may be modified using known physical and/or chemical treatment methods, such as for example corona treatment.
In accordance with a further embodiment of the present invention, there are provided filled articles (e.g., closed filled articles like welded bladders) comprising or fabricated from the multilayer films of the present invention as described previously herein, wherein the filling material may be either liquid or gaseous. Such filled articles are particularly suitable for accommodating water. Production of the filled articles proceeds using art-recognized joining process, such as for example high-frequency welding. Examples of filled articles according to the present invention, which comprise the multilayer films of the present invention include, but are not limited to water beds and hot/cold pads. The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations therein will be apparent to those skilled in the art. Unless otherwise specified, all parts and percentages are by weight.